Pervaporation of methanol/methyl tert‐butyl ether mixtures through agarose/hydroxyethylcellulose blended membranes

In this study, we investigated methanol (MeOH)/methyl tert‐butyl ether (MTBE) separation with hydroxyethylcellulose (HEC)/agarose blended membranes by applying a pervaporation technique. The membranes permeated MeOH in preference to MTBE from MeOH/MTBE mixtures. From pervaporation and sorption data, the permselectivity of HEC/agarose blended membrane was dominantly due to solubility selectivity. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 3408–3411, 2002     

用于脱除C5及MTBE中甲醇的渗透汽化膜研究

Several pervaporation membranes, cellulose acetate (CA), polyvinylbutyral (PVB), poly(MMA-co-AA), MMA-AA-BA, CA/PVB blend and CA/poly(MMA-co-AA) blend, were prepared, and their pervaporation properties were evaluated by separation of methanol/C5 or methanol/MTBE (methyl tert-butyl ether). The results shows that the CA composite membrane has a high separation performance (flux Jmenthanol =350g.m-2.h-1 and separation factor a > 400) for methanol/C5 mixtures, and the pervaporation characteristics of MMA-AA-BA copolymer membranes changes with the ratio of copolymer. For CA/poly(MMA-co-AA) blend membrane, the pervaporation performance is improved in comparison with CA or poly(MMA-co-AA) membrane. From the experiment of CA/PVB blend membranes for methanol/MTBE mixture, it is found that the compatibility of blends may affect the separation features of blend membrane.     

Study on swelling behavior and pervaporation properties of AA–MMA–BA copolymers for separation of methanol/MTBE/C5 mixtures

In this study, the copolymers with different ratios of AA(acrylic acid)–MMA(methyl methacrylate)–BA (butyl acrylate) are synthesized to prepare pervaporation membrane for the separation of methanol/MTBE (methyl tert‐butyl ether)/C₅ mixtures. Swelling experiment of these copolymers in pure methanol, MTBE, C₅, and methanol/MTBE mixtures are carried out, respectively. The results show that there is a strong interaction between MTBE and copolymer with high content of BA. The pervaporation characteristics of the membranes prepared with different copolymer are measured in the separation of methanol/MTBE mixture. The experimental results show that the pervaporation ability changes with swelling degree in the same direction. The copolymers are characterized by FTIR. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 87: 2267–2271, 2003     

用于脱除C5及MTBE中甲醇的渗透汽化膜研究

Several pervaporation membranes, cellulose acetate (CA), polyvinylbutyral (PVB), poly(MMA-co-AA),MMA-AA-BA, CA/PVB blend and CA/poly(MMA-co-AA) blend, were prepared, and their pervaporation properties were evaluated by separation of methanol/C5 or methanol/MTBE (methyl tert-butyl ether). The results shows that the CA composite membrane has a high separation performance (flux Jmethanol = 350 g.m-2.h-1 and separation factor α＞400) for methanol/C5 mixtures, and the pervaporation characteristics of MMA-AA-BA copolymer membranes changes with the ratio of copolymer. For CA/poly(MMA-co-AA) blend membrane, the pervaporation performance is improved in comparison with CA or poly(MMA-co-AA) membrane. From the experiment of CA/PVB blend membranes for methanol/MTBE mixture, it is found that the compatibility of blends may affect the separation features of blend membrane.     

Pervaporation separation of MTBE–methanol mixtures using cross‐linked PVA membranes

Poly(vinyl alcohol)(PVA)/poly(acrylic acid)(PAA) and PVA/sulfosuccinic acid (SSA) membrane performances have been studied for the pervaporation separation of methyl tert‐butyl ether (MTBE)/methanol (MeOH) mixtures with varying operating temperatures, amount of cross‐linking agents, and feed compositions. Typically, the separation factor, about 4000, and the permeation rate, 10.1 g/m²/h, were obtained with PVA/PAA = 85/15 membrane for MTBE/MeOH = 80/20 mixtures at 50°C. For PVA/PAA membranes, it could be considered that the flux is affected by the structural changes of the membranes due to the cross‐linking and the free carboxylic acid group also took an important role in the separation characteristics through the hydrogen bonding with PVA and the feed components leading to the increase of flux. The latter membrane of the 5% SSA membrane shows the highest separation factor of 2095 with the flux of 12.79 g/m²/h for MTBE/MeOH = 80/20 mixtures at 30°C. Besides the swelling measurements were carried out for pure MTBE and MeOH, and MTBE/MeOH = 90/10, 80/20 mixtures using PVA/SSA membranes with varying SSA compositions. It has been recognized that there are two factors, the membrane network and the hydrogen bonding in the swelling measurements of PVA/SSA membranes. These two factors act interdependently on the membrane swelling. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 1699–1707, 2000     

分离有机/有机混合物的PVA、CA系列膜及其渗透汽化性能研究(Ⅰ)膜材料与成膜工艺

依据溶度参数原则和分离甲基叔丁基醚(MTBE)/甲醇(MeOH)混合物的选择渗透性,选择了聚乙烯醇(PVA)为复合膜的分离层材料,聚丙烯腈(PAN)、醋酸纤维素(CA)系列为支撑层的膜材料.初步讨论了膜材料和复合膜结构对分离性能的影响,给出了用不同成膜工艺制备的膜性能,获得了可用于有机/有机体系分离的性能优良的PVA/PAN和PVA/CA复合膜,以及CTA中空纤维渗透汽化膜.     

Synthesis of MTBE in zeolite membrane reactors

A zeolite membrane was employed to selectively remove water from the reaction atmosphere during the gas-phase synthesis of methyl-tert-butyl ether (MTBE) from tert-butanol and methanol. This reaction was carried out over a bed of Amberlyst™ 15 catalyst packed on the inside of a zeolite tubular membrane. The results obtained with different hydrophilic membranes (mordenite or NaA zeolite) are presented. Prior to reaction, the zeolite membranes were characterized by measuring their performance in the separation of the equilibrium mixture containing water, methanol, tert-butanol, MTBE and isobutene. The results obtained with zeolite membrane reactors (ZMR) were compared with those of a fixed bed reactor (FBR) under the same operating conditions. MTBE yields obtained with the ZMR at 334 K reached 67.6%, under conditions where the equilibrium value without product removal (FBR) would be 60.9%.     

The effect of heat-treatment on the ultrafiltration performance of polyethersulfone (PES) hollow-fiber membranes

Polyethersulfone (PES) hollow-fiber membranes were prepared by the dry-wet spinning method and then heated in an oven at different temperatures to investigate the effect of heat-treatment on their ultrafiltration performance. It was found that the hollow-fiber membranes shrank by heat treatment, as evidenced by a decrease in flux and an increase in solute separation, although there was no visible change in the hollow-fiber dimension. The best results were obtained when the hollow fibers were heated at 150°C. A further investigation was made on the effect of the heating period, while the temperature was fixed to 150°C. It was found that the best combination of the temperature and the heating period was 150°C and 5 min.     

Thin film composite membranes with desirable support layer for MeOH/MTBE pervaporation

A comprehensive study was performed on a new application of thin film composite membranes and selecting a stable sublayer for them as pervaporation membranes in organic solvent separation. For this purpose, four different polymeric sublayers of polyethersulfone (PES), cellulose acetate, polyacrylonitrile, and polyetherimide were prepared, and the interaction of methanol (MeOH) and methyl tert butyl ether (MTBE) with them was investigated. The contact angle results, scanning electron microscopy images, and swelling and mechanical strength measurements obviously displayed the effect of immersion in organic solvents on the sublayers. Finally, a polyamide active layer was subsequently deposited on the PES membrane surface as the stable sublayer via interfacial polymerization based on a multistep statistical optimization strategy involving fractional factorial design and a response surface method. The prepared TFC membranes were tested in the pervaporation of a MeOH/MTBE mixture and exhibited excellent performance compared with the current membranes in this context. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47519.     

Pr0.6Sr0.4Co0.2Fe0.8O3-δ中空纤维陶瓷膜的制备及其透氧性能

采用改进的溶胶-凝胶法制备了一系列陶瓷粉体Pr1-xSrxCo1-yFeyO3-δ(x=0.2、0.4、0.6;y=0.2、0.4、0.6、0.8).运用相转化/烧结技术制造出了Pr0.6Sr0.4Co0.2Fe0.8O3-δ(PSCF6428)中空陶瓷纤维膜.用热分析、X射线衍射仪、扫描电镜、X射线能谱等技术对制备的...     

Preparation and characterization of methanol selective membranes based on polyheteroarylene − Cu(I) complexes for purification of methyl tertiary butyl ether

A comparative study of metal ? polymer complexes of Cu(I) with polybenzoxazinoneimide (PBOI) and its prepolymer imide‐containing polyamic acid (PAA) as novel membrane materials for methyl tertiary butyl ether (MTBE) purification was undertaken. The structure, physical parameters and transport properties were characterized in detail to analyse the separation performance of the membranes and obtain new knowledge on the interdependence of the chemical structure and physical data with transport parameters. Thermally initiated conversion of PAA ? Cu(I) to PBOI ? Cu(I) was studied by TGA and DSC. The thermal conversion increases the polymer glass transition temperature and membrane density. Both polymers were applied to pervaporation separation of MTBE from methanol impurities. Membranes based on PAA are highly effective in MTBE purification and preferably permeate methanol. The transport properties of PAA ? Cu(I) membrane are compared with those of known membranes. © 2017 Society of Chemical Industry     

Pervaporation separation of methanol/methyl tert‐butyl ether with poly(lactic acid) membranes

Poly(lactic acid), as a natural source polymer, was used to prepare pervaporation dense membranes. The performance of these membranes for the separation of the methanol (MeOH)/methyl tert‐butyl ether (MTBE) mixtures was investigated. The effects of different operating conditions, including the feed concentration of MeOH, temperature, and flow rate, were examined. Several characterization tests were performed as well. The swelling results, scanning electron microscopy images, contact angles, and mechanical strength measurements are presented. These membranes were found to be selective to MeOH, particularly for traces of MeOH in MTBE with a separation factor of more than 30. There was a small decrease in the separation factor when the feed temperature was increased; meanwhile, the total flux increased to some extent. This could be explained with respect to the thermal motions of the polymer chains and the permeating molecules. With an increase in the feed flow rate, both the selectivity and total flux increased because the concentration and temperature polarizations decreased. At higher flow rates, the feed components were homogeneously distributed over the membrane surface, whereas there may have been a concentration or temperature gradient at lower flow rates. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

An experimental study on the application of polymer membranes to the catalytic decomposition of MTBE (methyl tert.-butyl ether)

In this experimental study, the methyl tert.-butyl ether (MTBE) decomposition was carried out in various inert membrane reactors composed of H₃PW₂O₄₀ and a polymer membrane. Polycarbonate (PC), polyarylate (PA) and cellulose acetate (CA) membranes were used in the membrane reactor. It was revealed that all the tested polymer membranes showed larger permeability of methanol than that of either MTBE or isobutene, and the membrane reactor showed better performance than the corresponding fixed bed reactor. The perm-selectivity of methanol/MTBE was in the order of CA > PC > PA, and the permeation ratio of product/MTBE was in the order of CA > PA > PC. Among the membrane reactors tested CA membrane reactor showed the best performance. The enhanced performance of the membrane reactor was mainly due to the selective permeation of methanol that made a methanol-deficient phase suppressing MTBE synthesis reaction in the reversible reaction.     

SOME OBSERVATIONS ON THE PERFORMANCE OF HOLLOW-FIBER SUPPORTED LIQUID MEMBRANES FOR Co-Ni SEPARATIONS*

The performance of hollow-fiber supported liquid membranes (HFSLM) for Co/Ni separation, utilizing a dialkylphosphinic acid as Co('II) selective carrier, has been studied. The primary objective of the study was to obtain practical information concerning the life-time of HFSLMs and how to extend it by fiber re-impregnation techniques. Results demonstrating the feasibility of concentration/separatlon processes are.alao reported.     

Development of poly(vinylidene fluoride) hollow-fiber membranes for the treatment of water/organic vapor mixtures

Attempts were made to spin hollow-fiber membranes from poly(vinylidene fluoride) (PVDF) material by the dry–wet phase inversion method. Hollow fibers so prepared were characterized for various parameters and by electron microscopic techniques. Membranes were also tested for the separation of water/1-propanol mixtures in vapor phase. It was found that the hollow fibers were water selective despite the fact that PVDF material is hydrophobic. Intrinsically organic selective property of PVDF material was proved by coating a porous polyetherimide membrane with a PVDF layer, which resulted in enhancement of 1-propanol permeation while suppressing the permeation of water. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 65:1263–1270, 1997     

Copolyimide molecular brushes with poly(methacrylic acid) side chains as additive to polyphthalamide membrane: Organization,physical, and transport properties

Macromolecules of complex architecture find application as modifiers of commercial polymeric membrane materials. In this work, copolyimide molecular brushes (coPI) composed of polyimide backbone and poly(methacrylic acid) side chains were used to modify poly(m-phenylene iso-phthalamide) (PPA). Structure, physical, mechanical, and transport properties of dense nonporous PPA/coPI membranes containing up to 10 wt% coPI were studied. The effect of included coPI on the membrane structure was estimated using atomic force microscopy and mechanical tests. The coPI modifier contributes to the additional formation of free volume elements evenly distributed throughout the membrane. Transport properties of PPA/coPI membranes were investigated via sorption tests and pervaporation separation of methanol (MeOH) and methyl tert-butyl ether (MTBE) mixtures. The inclusion of coPI modifier in the PPA membrane leads to an increase in the total flux of the membrane. The highest separation factor was found for the PPA/coPI membrane containing 10 wt% coPI; transport properties of the best membrane were compared with the literature data on separation of the azeotropic MeOH–MTBE mixture.     

Gas permselection properties in silicone-coated asymmetric polyethersulfone membranes

The gas permeation properties of H₂, He, CO₂, O₂, and N₂ through silicone-coated polyethersulfone (PESf) asymmetric hollow-fiber membranes with different structures were investigated as a function of pressure and temperature and compared with those of PESf dense membrane and silicone rubber (PDMS) membrane. The PESf asymmetric hollow-fiber membranes were prepared from spinning solutions containing N-methyl-2-pyrrolidone as a solvent, with ethanol, 1-propanol, or water as a nonsolvent-additive. Water was also used as both an internal and an external coagulant. A thin silicone rubber film was coated on the external surface of dried PESf hollow-fiber membranes. The apparent structure characteristics of the separation layer (thickness, porosity, and mean pore size) of the asymmetric membranes were determined by gas permeation method and their cross-section morphologies were examined with a scanning electron microscope. The results reveal that the gas pressure normalized fluxes of the five gases in the three silicone-coated PESf asymmetric membranes are nearly independent of pressure and did not exhibit the dual-mode behavior. The activation energies of permeation in the silicone-coated asymmetric membranes may be larger or smaller than those of PESf dense membrane, which is controlled by the membrane physical structure (skin layer and sublayer structure). Permselectivities for the gas pairs H₂/N₂, He/N₂, CO₂/N₂, and O₂/N₂ are also presented and their temperature dependency addressed. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 66: 837–846, 1997     

渗透汽化膜分离MeOH/MTBE混合物的传质分析——单组分在膜中的扩散

用石英晶体微平衡法测定了298.15 K、305.75 K、312.95 K下MeOH（甲醇）和MTBE（甲基叔丁基醚）在CA（醋酸纤维素）膜中的吸着平衡数据和吸着动力学数据.结果表明：MeOH和MTBE在CA膜中的传质过程属于Fick扩散类型;MeOH在CA膜中的平衡吸着量和扩散系数都比MTBE大,说明CA膜对MeOH/MTBE混合物有较好的分离性能;同一吸着温度下,吸着速度和平衡吸着量均随着吸着蒸气压的升高而升高;可用Eyring的扩散“空穴”理论解释MeOH和MTBE在膜中的扩散行为.     

Pervaporation separation of methyl tert-butyl ether/methanol mixtures using a high-performance blended membrane

For the separation of methyl tert-butyl ether (MTBE) and methanol mixtures, we investigated the pervaporation performance of a blend membrane made from cellulose acetate and cellulose acetate hydrogen phthalate. At first the influence of the blend composition was studied with a certain feed mixture. We found that all the tested membranes permeate methanol preferentially. The selectivity increases and the permeation rate decreases with increasing cellulose acetate content in the blend. Therefore, an optimal blend composition of 30 wt % in cellulose acetate was chosen to evaluate the influence of the feed composition and the experimental temperature on the pervaporation performance. When the feed temperature or the methanol content in the feed increases, the permeation rates are greatly enhanced and the selectivity decreases. However, the temperature effect is more significant at low methanol content in the feed and becomes negligible at high methanol content in the feed where plasticity effects prevail. A comparison, carried out with all the membranes until now used for the separation of MTBE/methanol mixtures, showed that the blended membrane studied in this present work presents good permselective properties. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 64: 875–882, 1997     

Surface Modification of Ready-to-Use Hollow Fiber Ultrafiltration Modules for Oil/Water Separation

Reusing wastewater from oil-related industries is becoming increasingly important, especially in water-stressed oil-producing countries. Before oily wastewater can be discharged or reused, it must be properly treated, e.g., by membrane-based processes like ultrafiltration. A major issue of the applied membranes is their high fouling propensity. This paper reports on mitigating fouling inside ready-to-use ultrafiltration hollow-fiber modules used in a polishing step in oil/water separation. For this purpose, in-situ polyzwitterionic hydrogel coating was applied. The membrane performance was tested with oil nano-emulsions using a mini-plant system. The main factors influencing fouling were systematically investigated using statistical design of experiments.